A considerable number of methods for production of alkylamine products have been proposed and a number of them have been commercially utilized. The present invention particularly concerns the production of lower alkylamines and alkyldiamines by the catalytic amination of lower aliphatic alkane derivatives including mono- and polyhydric alcohols, alcoholamines, and compounds from which these alcohols are derived, including alkoxides, ketones and alkyleneimines.
The catalytic amination of alcohols is a process which has been long recognized in the prior art. It generally concerns the reaction of alcohol with ammonia in the presence of a hydrogenation catalyst and usually in the presence of hydrogen.
The most difficult problem in the manufacture of amines by this and other proposed processes is that the chemical synthesis reactions used also form substantial amounts of byproducts, which are of considerably less value and as a result often render the synthesis inefficient and not commercially feasible.
The most desirable amine products generally are those products wherein an amine group replaces the non-amine functional group or groups in the alkyl starting material without any further modification of the starting material. Most heavier, more highly substituted amines and heterocyclic nitrogen compounds can be further synthesized from these preferred alkylamines and diamines. A synthesis of these heavier, substituted, and heterocyclic amines directly from the alkyl starting materials usually yields other unwanted by-products.
The amine products produced in accordance with the present invention have many uses. In addition to their use as intermediates for synthesizing other chemical materials, they are utilized in fungicides and insecticides.
For convenience in the description of the invention hereinbelow, the amination of ethylene glycol and monoethanol amine to ethylenediamine and other products will be most comprehensively discussed, although the present invention is not limited to these starting materials.
The amination of ethylene glycol may be illustrated by the following chemical formula with the primary products being monoethanolamine (MEA), ethylenediamine (EDA), and piperazine (also termed diethylenediamine, DEDA): ##STR1##
Numerous other chemical reactions are known for producing alkylamines and diamines. For example, in the synthesis of ethylenediamine, the following reactions have been proposed: the hydrolysis of ethylene urea; reductive amination of formaldehyde cyanohydrin; the reduction of cyanogen; the reduction of 1,2-dinitroethane; and the amination of chloroacetylchloride followed by reduction. None of these chemical processes appear to have been operated on a commercial scale because of the process requirements and costs of raw materials.
One of the most widely used commercial processes for producing ethylenediamine today involves a reaction of ethylenedichloride with aqueous ammonia. The ethylenedichloride is reacted with aqueous 30 to 40% ammonia to produce a dilute aqueous solution of amines. Sodium hydroxide is then added to neutralize the hydrochloric acid formed in the ammonia-ethylene dichloride reaction. This neutralization step forms additional water and gives rise to by-product sodium chloride. An illustration of the approximate distribution or profile of products produced by such a process is as follows:
______________________________________ Products Wt. % of Production ______________________________________ Ethylenediamine (EDA) 41% Diethylenetriamine (DETA) 25% Triethylenetetramine (TETA) 10% Tetraethylenepentamine (TEPA) 8% Pentaethylenehexamine (PEHA) 13% Polyamine Heavies (PAH) 13% Piperazine (DEDA) 1.5% Aminoethylpiperazine (AEP) 1.5% ______________________________________
About 2.5 lbs. of sodium chloride is produced per lb. of the amines produced.
Although the product distribution is commercially feasible, the presence of chlorine in the system, including in the corrosive form of hydrogen chloride, causes expensive maintenance costs. Moreover, recovery of the desired amine products from the salt-containing aqueous solution is difficult and the disposal of the large quantities of salt is an ever increasing environmental problem. The cost of the starting materials also has been a discouraging factor.
A method which has recently emerged commercially is the reduction of amino acetonitrile to form ethylenediamine. Although this process, according to the literature can be operated to produce as much as 90% ethylenediamine in the amine yield, the expense of the starting materials in the process and other economic considerations do not make this process commercially attractive.
As indicated above, the catalytic amination of alkane derivatives including aliphatic alcohols and aminoalcohols has been the subject of much investigation and prior art literature. The applicant has now discovered a new catalyst which is both more active and more selective than previously known catalysts for carrying out amination processes. It should be noted that there are numerous materials which have the ability to catalyze such amination processes, but the mere ability to catalyze is far from sufficient to accord a catalyst one of commercial significance.
U.S. Pat. No. 2,861,995 describes a method of converting ethanolamine to various nitrogen-containing products by using a metal hydrogenation catalyst comprising one or more of nickel, cobalt, copper chromite, catalytic noble metals such as platinum and palladium, and Raney nickel and Raney cobalt. They may be supported on a carrier such as alumina.
U.S. Pat. No. 3,068,290 describes a process for converting ethanolamine to ethylenediamine by using a hydrogenation catalyst, such as described above, in a reaction which is in the liquid phase, under autogenous pressure. The patent also describes a preferred catalyst which is a combination of nickel and magnesium oxides (Ni-MgO), obtained by thermal decomposition of coprecipitated nickel and magnesium formates or oxalates.
U.S. Pat. No. 3,137,730 teaches the conversion of ethylene glycol by using a supported catalyst comprising nickel and copper. U.S. Pat. No. 3,270,059 teaches an amination process in the presence of a supported catalyst which is produced by sintering oxygen compounds of either nickel or cobalt at temperatures in excess of 700.degree. C and reducing the sintered metal compound by treatment with hydrogen. U.S. Pat. No. 3,766,184 describes a catalyst containing iron with either nickel, cobalt or mixtures thereof. Ruthenium catalysts are also referred to in this and other patents as useful in amination processes.
None of the catalysts heretofore known have been commercially successful because of one or more inadequacies. Modern commercial catalytic processes require catalysts to be more than active, i.e., yield high conversions in the chemical reactions they catalyze. In the case of amination processes where numerous competing reactions occur yielding many by-products, it is important for the catalyst to have good selectivity or the ability to afford a high yield of useful product with a concomitant small yield of undesired product. The optimum reaction conditions including temperature, pressure and relative proportions of reactants, as well as reaction time, may be determined by the catalyst, and in so doing may affect the economics of the whole process. The cost of the catalyst, its method of preparation and its effective life as well as its physical properties may be determinative of a successful, viable process.
The applicant has now discovered a new catalyst containing nickel and rhenium, supported on a material selected from .alpha.-aluminas, silica, silica-aluminas, kieselguhrs and diatomaceous earths which have improved properties over those catalysts heretofore known for catalyzing the amination of aliphatic lower alkyl derivatives.